Additives for hydrocarbonaceous materials

ABSTRACT

Additive formulations for use in hydrocarbonaceous materials and particularly in petroleum distillates such as gasoline which provide improved properties thereto will comprise a mixture of the reaction product of an epihalohydrin and a primary amine containing from 14 to 22 carbon atoms and the reaction product of an epihalohydrin and an N-alkyl polyamine containing from 14 to 22 carbon atoms.

United States Patent Gattuso 1 Dec. 30, 1975 ADDITIVES FOR HYDROCARBONACEOUS 3,705,l09 l2/l972 Hansler et al 44/72 MATERIALS 3,755,171 8/1973 Cyba et a1 252/515 R 3,756,795 9/l973 Rosenwald 44/62 1 lnvenwv Marlon J- Gamlso, Hoffman 3,813,228 5 1974 Geiser 252 515 R Estates, Ill.

[73] Assignee: Universal Oil Products Company, Prim ry ExaminerDelbert E. Gantz Des Plaines, lll. Assistant Examiner-l. Vaughn Attorney, Agent, or Hum-James R. Hoatson, Jr.; [22] 1974 Raymond H. Nelson; Wllliam H. Page, [I [21] Appl. No.: 521,981

ABSTRACT [52] Cl 52 516 I ii gr Additive formulations for use in hydrocarbonaceous materials and particularly in petroleum distillates such [51] CloM 1/32 CIOM 3,26 g as gasoline which provide improved properties thereto D will comprise a mixture of the reaction product of an [58] Field of Search 44422711164013, epihalohydrin and a primary amine containing from 14 to 22 carbon atoms and the reaction product of an epihalohydrin and an N-alkyl polyamine containing [56] Rderences cited from 14 to 22 carbon atoms.

UNITED STATES PATENTS 8/1972 Rosenwald 44/72 12 Claims, No Drawings ADDITIVES FOR HYDROCARBONACEOUS MATERIALS This invention relates to additive formulations for use in hydrocarbonaceous compounds. More particularly, the invention is concerned with additive formulations for use in petroleum distillates such as gasoline whereby said distillate will have advantageous physical properties imparted thereto.

Petroleum distillates such as gasoline, naphtha, fuel oils, diesel oils, jet fuel, kerosene, lubricating oils, cutting oils, soluble oils, slushing oils, rolling oils, which may be mineral, animal or vegetable origin, etc., will tend, during storage or in use, to undergo deterioration with the concurrent formation of sediment, undesirable discoloration, etc. The formation of sediment is objectionable due to the fact that said sediment will tend to plug strainers, burner tips, injectors, etc. It is also well known in the art that, at temperatures ranging from about 30" to about 60 F. and at periods of relatively high humidities, such stalling has been encountered under idling or low load conditions. This stalling is caused by the air-borne moisture undergoing freezing due to the refrigerating effect which is encountered in normal fuel vaporization within the carburetor. The ice is formed on the throttle plate and adjacent carburetor walls thereby restricting the narrow air openings and causing the engine to stall. This icing problem is of increasing importance because of the design of newer automobiles. For example, for many years automobiles have not been equipped with a manual throttle and therefore the operator of the car no longer is able to increase the idling speed during the warm-up period to prevent such stalling. Furthermore, the use of automatic transmissions adds to the problem inasmuch as the idle speed must be kept relatively low to avoid creeping and, accordingly, the idle speed is not sufficiently fast to avoid stalling due to icing. Still another development which appears to add to this problem is the increased volatility of commercial gasolines, because more frequent stalling is encountered with the more volatile fuels. In this respect, it has now been discovered that an additive may be prepared which, when used in petroleum distillates such as gasolines, either leaded or unleaded, or fuel oils will protect against icing stalls and, in addition, will also provide a detergent property which will reduce any deposits which will tend to build up on sensitive parts such as carburetors in an internal combustion engine.

Due to the inherent miscibility problems as well as a shortage of solvents which currently plagues the industry, it is desirable to utilize additives for petroleum distillates which may be either liquid or solid in the pure state and at ambient temperatures. lt has now been discovered that, by forming a mixture of two separate and distinct reaction products, it is possible to obtain a solid petroleum additive which will impart the desirable characteristics of both carburetor detergency and de-icing to distillates such as gasoline. It is of particular importance that a combination of both solubility and melting points is obtained so that the aforesaid solubility and melting point are at a maximum stage. In this respect, it is desirable to prepare compounds possessing the highest number of carbon atoms on saturated alkyl chains which will raise the melting point of the final product to such a degree so that good storage stability is present. However, it is known in the art that materials which possess lower carbon atom alkyl chains also possess good solubility characteristics. Therefore, it is desirable that mixtures of various materials must be obtained in order to prepare a solid additive which possesses the best combination of solubility and melting point.

It is therefore an object of this invention to provide an additive for petroleum distillates which will protect said distillates against deterioration thereof.

A further object of this invention is to provide a solid additive for petroleum distillates which will possess the maximum desirable properties of solubility and stability, said additive being used to impart desirable physical characteristics to the aforesaid distillates.

In one aspect an embodiment of this invention resides in a solid additive comprising a mixture of from about 1 to about 50 percent by weight of the reaction product of an epihalohydrin and a primary amine containing from 14 to 22 carbon atoms and from about 50 to about 99 percent by weight of the reaction product of an epihalohydrin and an N-alkyl-l,3-diaminopropane containing from 14 to 22 carbon atoms in the alkyl chain.

A specific embodiment of this invention is found in a solid additive for petroleum distillates which comprises a mixture of about 30 percent by weight of the reaction product of epichlorohydrin and a primary amine comprising a mixture of 4% C alkyl amines, 29% C alkyl amines and 67% C alkyl amines and 70 percent by weight of the reaction product of epichlorohydrin and an N-alkyl-l,3-diaminopropane comprising a mixture of 4% C 29% C and 67% C N-alkyl-l ,3- diaminopropanes.

Other objects and embodiments will be found in the following further detailed description of the present invention.

As hereinbefore set forth, the present invention is concerned with a solid additive, preferably for petroleum distillates, which will be useful for imparting improved detergent and anti-icing properties to the distillate. By utilizing a mixture of two polymeric reaction products resulting from (I) the reaction between an epihalohydrin and a primary alkyl amine possessing a certain carbon atom length chain and (2) an epihalohydrin with a N-alkyl-l,3-diaminopropane in which the alkyl chain possesses a certain number of carbon atoms, it is possible to obtain a product which will itself possess the necessary and desirable balance between solubility and melting characteristics. These solubility and melting characteristics are afforded by a judicious choice of the number of carbon atoms in the alkyl chains which are present in both the primary amine and the substituted l,3-diaminopropane, specific examples of these compounds being hereinafter set forth in greater detail.

The first component of the additive mixture of the present invention, namely, the polymeric reaction product of an epihalohydrin and a primary amine is prepared by effecting the reaction at temperatures ranging from about 20 to about C. Illustrative examples of primary alkyl amines in which the alkyl portion of the compound contains from about 14 to about 22 carbon atoms will include tetradecyl amine, pentadecyl amine, hexadecyl amine, heptadecyl amine, octadecyl amine, nonadecyl amine, eicosyl amine, heneicosyl amine and docosyl amine. Conveniently, the long chain amines may be prepared from fatty acids or, more particularly, mixtures of fatty acids formed as products or by-products. Such mixtures are available commercially, generally at lower prices and as an advantage which may be exploited by the present invention, mixtures of these long chain amines may be used without the necessity of separating individual amines in pure state. As an illustration of these mixtures, it is possible to utilize various commercial materials which are sold under the tradenames Kemamine P-970 which is a mixture of primary amines containing 67% C alkyl amines, 29% C alkyl amines and 4% C alkyl amines; Kemamine P-l50 which contains about 20% C alkyl groups, 30% C alkyl groups and 50% C C alkyl groups", and Kemamine P-l90 which contains about C alkyl groups and 90% C -C' alkyl groups.

As hereinbefore set forth, the amine compound is reacted with an epihalohydrin compound, the preferred epihalohydrin compound being epichlorohydrin. Other epichlorohydrin compounds which may be employed will include l,2-epoxy-4-chlorobutane, 2,3- epoxy-4-chlorobutane, l,2-epoxy-5-chloropentane, 2,3-epoxy-5-chloropentane, l,2-epoxy-6-chlorohexane, 2,3-epoxy-6-chlorohexane, etc. Generally speaking the chloro derivatives are preferred, although it is understood that the corresponding bromo and iodo compounds may be utilized in the present invention. While in some instances epidihalohydrin compounds may be used, it is understood that the different epihalohydrin and epidihalohydrin compounds are not necessarily equivalent in the same or different substrates and that, as hereinbefore set forth, epichlorohydrin constitutes the preferred compound.

In general, one or two moles of amine compound is reacted with one or two moles of epihalohydrin compound. It is understood that, in some cases, an excess of amine or of epihalohydrin may be supplied to the reaction zone in order to ensure complete reaction, the excess being removed subsequently in any suitable manner. When two moles of amine are reacted per mole of epihalohydrin compound, the amine may comprise the same or different amine compound.

The desired quantity of alkyl amine and epihalohydrin compounds may be supplied to the reaction zone and therein reacted, although generally it is preferred to supply one reactant to the reaction zone and then introduce the other reactant step-wise. Thus, usually it is preferred to supply the alkyl amine to the reaction zone and to add the epihalohydrin compound step-wise with stirring. When it is desired to react two different alkyl amines with the epihalohydrin compound, one of the amines is supplied to the reaction zone, the epihalohydrin compound added gradually, and the reaction completed, followed by the addition of the second alkyl amine. Generally it is preferred to utilize a solvent and, in the preferred embodiment, a solution of the alkyl amine in a solvent and a separate solution of the epihalohydrin compound in a solvent are prepared, and these solutions are then commingled in the manner hereinbefore set forth. Any suitable solvent may be employed, a particularly suitable solvent comprising an aromatic type such as benzene, toluene, xylene, etc. Other solvents such as alcohols including ethanol, propanol, butanol, etc., are also desirable.

As hereinbefore set forth, the reaction is effected at temperatures which generally will be within the range of from about 20 to about 150 C. and preferably within the range of from about 50 to about I25 C. If so desired, higher reaction temperatures ranging from about to about 200 C. or more and preferably of from about 50 to about l00 C. may be employed, with 4 a combination of superatmospheric pressures and elevated temperatures increasing the reaction velocity.

Either before or after removal of the reaction product from the reaction zone, the product is treated to remove the halogen, generally in the form of an inorganic halide salt as, for example, the hydrogen halide salt. This may be effected in any suitable manner and may be accomplished by reacting the product with a strong inorganic base such as sodium hydroxide, potassium hydroxide, etc., to form the corresponding metal halide, the removal of the halogen being effected at substantially the same conditions as were employed in the reaction between the alkyl amine and the epihalohydrin. Upon completion of this reaction, the metal halide is removed in any suitable manner such as by filtration, centrifugal separation, etc. In addition, it is to be understood that the reaction product is also heated to a sufficient temperature to remove alcohol and water, the removal of said alcohol and water being effected either before or after the treatment to remove the inorganic halide.

The second component of the additive formulation will comprise the polymeric reaction product of an epihalohydrin and an N-alkyl polyamine, the preferred N-alkyl polyamines comprising N-aklyl-l,3-diaminopropanes in which the alkyl group contains from 14 to 22 carbon atoms. Illustrative examples of these compounds will include N-tetradecyl-l ,3-diaminopropane, N-pentadecyl-l ,3-diaminopropane, N-hexadecyl-l ,3- diaminopropane, N-heptadecyl-l,3-diaminopropane, N-octadecyl-l ,3-diaminopropane, N-nonadecyl-l ,3- diaminopropane, N-eicosyl-l,3-diaminopropane, N- heneicosyl-l ,S-diaminopropane, N-docosyl-l ,3- diaminopropane, etc. As in the case of the primary amines, mixtures of these N-alkyl-l ,3-diaminopropanes are commercially available and may be advantageously used for the purposes of the present invention. Some examples of these mixtures will include Kemamine D-970 which is N-hydrogenated tallow-l,3-diaminopropane and predominates in alkyl groups containing from C to C carbon atoms each, there being about 67% of the C alkyl groups, 29% of the C alkyl groups with about 4 percent of alkyl groups containing 14 carbon atoms. Another mixture which is available is sold under the tradename Kemamine D-l50" which contains about 20% C alkyl groups, 30% C alkyl groups and about 50 percent of alkyl groups containing from 20 to 22 carbon atoms or Kemamine D-l which contains about 10% C alkyl groups and about 90% C to C alkyl groups.

While the N-alkyl-l ,3-diaminopropanes are preferred compounds of this class, it is also contemplated within the scope of this invention that suitable N-alkyl ethylenediamines, N-alkyl-l,3-diaminobutanes, N- alkyll ,4-diaminobutanes, N-alkyl-l ,3-diaminopentanes, N-alkyl-l ,4-diaminopentanes, N-alkyl-l ,5- diaminopentanes, the isomeric N-alkyl-l ,3- diaminohexanes, etc., may also be employed, but not necessarily with equivalent results.

As in the case of the primary alkyl amines and the epihalohydrins, similar conditions for the reaction be-. tween the epihalohydrin and the N-alkyl polyamines are employed in order to obtain the desired reaction product.

The two components of the additive formulation of the present invention are admixed by any means known in the art such as stirring, agitation, etc., and will be present in the formulation in such a manner so that the polymeric reaction product of the epihalohydrin and the primaryalkyl amine is present in an amount in the range of from about I to about 50 percent by weight and the polymeric reaction product between the epihalohydrin and the N-alkylpolyamine will be present in an amount in the range of from about '50 to about 99 percent by weight of the finished additive product.

In general, the additive formulation will be present in the petroleum distillate in an amount in the range of from about I to about IOOO'ppm by weight of the petroleum distillate, although it is contemplated within the scope of this invention that lesser or greater amounts of the formulation may be present, a specific amount being dependent upon the particular petroleum distillate which acts as a substrate for the formulation. As will hereinafter be shown in the appended examples, the presence of the additive formulation in the petroleum distillate will provide improved activity in carburetor detergency and de-icing activity over petroleum distillates which do not contain the additive formulation of the present invention.

The following examples are given to illustrate the additive formulations of the present invention and the ability of the same to provide improved properties to petroleum distillates. However, these examples are not intended to limit the generally broad scope of the present invention in strict accordance therewith.

EXAMPLE In this example a'polymeric reaction product was obtained by admixing L0 mole of epichlorohydrin with 1.0 mole of a primary alkyl amine in a xylene solvent, said mixture containing 4 percent of a primary amine containing 14 carbon atoms in the alkyl'chain, 29 percent of a primary alkyl amine which contained 16 carbon atoms in the alkyl chain and 67 percent of a primary alkyl amine which contained 18 carbon atoms in the chain. The reaction mixture was worked up in a manner as described previously and the product recovered by precipitation from methanol. In addition, a second polymeric reaction product was also prepared by admixing l.25 moles of epichlorohydrin with 1.0 mole of N-alkyl-l,3-diaminopropane which possesses the same composition as to percentages of C C and C carbon atom chains as did the primary amine in a xylene solvent. The reaction mixture was worked up in a manner as described previously and the product recovered by precipitation from methanol. The resulting solid reaction products were then admixed so that the final blend contained 30 percent by weight of the polymeric reaction product of a primary alkyl amine and epichlorohydrin and 70 percent by weight of the polymeric reaction product of the diamine and epichlorohydrin.

The aforementioned blend was utilized as an additive for gasoline to determine the operability of the same to act as a carburetor detergent. The additive was added to both regular base and premium base gasoline in a concentration of 50 ppm. A standard carburetor detergency test was run in which a six cylinder engine on a test stand was run through a specific test cycle during a standard hour period of time, the speed of the engine being varied from idle to various speeds up to about 60 miles per hour and return. In the test, a clean carburetor throat body was placed between the carburetor and the intake manifold. The throat body was constructed in such a manner so that it could be removed, inspected and replaced by another throat body. The throat body consisted of two halves for easy removal and contained a butterfly valve. During the first 5-hour test cycle, gasoline which did not contain the fuel additive of the present invention was sent through the engine. At the end of the 5-hour period, the throat body was removed and replaced with a clean throat body. The standard S-hour test cycle was then repeated utilizing a fuel which contained the aforementioned blend in an amount of 50 ppm. At the end of this second test cycle, the throat body was again removed and compared to the throat body which was utilized in the test cycle which was run using gasoline which contained no additive. It was found that the gasoline which contained the blend of the present invention reduced deposits by 95 percent on the upper portion and by 99 percent on the lower portion of the throat body.

EXAMPLE [I In a manner similar to that set forth in Example I above, a fuel additive blend was prepared by obtaining a polymeric reaction product which resulted from the reaction between epichlorohydrin and a primary alkyl amine which consisted of IO percent alkyl amines containing 18 carbon atoms in the alkyl chain and percent of an alkyl amine which contained from 20 to 22 carbon atoms in the chain. Likewise, epichlorohydrin was reacted with an N-alkyl-l,3-diaminopropane in which the alkyl chains contained the same proportions of carbon atoms, that is, 10 percent of alkyl chain con taining 18 carbon atoms and 90 percent of alkyl chains containining from 20 to 22 carbon atoms. The reaction products resulting from the aforesaid reactions were blended so that the final blend contained 30 percent by weight of the former reaction product and 70 percent by weight of the latter reaction product. 7 In like manner 50 ppm of this blend was added to both regular base'and premium base gasoline. A similar carburetor detergency test using a standard S-hour test cycle was run in which the regular base and premium base gasoline were passed through a six cylinder engine equipped with a removable throat body in the carburetor and the test was repeated using the gasoline which contained the additive. It was found that the use of gasoline containing the additive resulted in a reduction of deposits by percent on the upper portion and by 99 percent on the lower portion of the throat body as compared to the deposits laid down when utiliziing gasoline which contained no additive.

EXAMPLE III In this example a polymeric reaction product is prepared by reacting epichlorohydrin with a primary alkyl amine composed of a mixture of 20 percent alkyl amines containing I6 carbon atoms in the chain, 30 percent of alkyl amines containing I8 carbon atoms in the chain and 50 percent of alkyl amines containing from 20 to 22 carbon atoms in the chain. A second reaction product is obtained by reacting equimolar portions of epichlorohydrin with an N-alkyl-l ,3- diaminopropane which is composed of a mixture of 20% C alkyl l,3-diaminopropane, 30% C alkyl 1,3- diaminopropane and 50% of from C to C alkyl 1,3- diaminopropane. A gasoline additive blend is prepared by admixing 50 percent by weight of each of the polymeric reaction products and the additive is then added to gasoline in an amount of 50 ppm. The results which are obtained when using this additive in a gasoline which is used as the fuel in a carburetor detergency test 7 will result in a reduction of deposits on the upper portion and lower portion of the throat body of over 90 percent when compared to the deposits laid down on the throat body when using a gasoline which does not contain this additive.

EXAMPLE IV The anti-icing properties of the distillate additives which comprise blends set forth in Examples I, ll and Ill above are determined by using a carburetor icing demonstration apparatus. This apparatus consists of a vacuum pump equipped so that cold moisture-saturated air from an ice tower is drawn through a simulated carburetor. The gasoline sample passed from a fuel reservoir through a flow meter into the carburetor at a rate of [.5 lblhr. The air from the ice tower is passed into the carburetor at a flow rate of [4.4 lblhr at a temperature of 40 F. in addition, the manifold vacuum is 9.5 inches of mercury at the start and 12.5 inches at the end of the test. Evaporation of the gasoline in the carburetor further cools the cold, moist'air, with resulting ice formation on the throttle plate. The time in seconds is mea sured until a drop of 3 inches of mercury vacuum oc curs which indicates stalling conditions. The regular type gasoline which is used in this experiment will reach stalling conditions within about 16.5 seconds. In contrast to this, when an additive formulation in a concentration of about 30 ppm is added to the gasoline, it will be found that the stalling times of each of the additives, as exemplified by the additives prepared in Examples I, II and Ill above, will be greater than the 16.5 seconds.

In like manner, when the solid additives exemplified in the preceding examples are added to other petroleum distillates such as fuel oil and lubricating oil, it will be found that said additives will impart detergent properties to these distillates whereby the amount of deposits found on burner tips or injectors in the case of l. A solid additive comprising a mixture of from about I to about 50 percent by weight of the reaction product of an epihalohydrin and a primary amine containing from 14 to 22 carbon atoms, and from about 50 to about 99 percent by weight of the reaction product of an epihalohydrin and an N-alkyl-l ,3-diaminopropane containing from 14 to 22 carbon atoms in the alkyl chain.

2. The solid additive as set forth in claim 1 being added to a petroleum distillate.

3. The petroleum distillate as set forth in claim 2 being gasoline.

4. The petroleum distillate as set forth in claim 2 being fuel oil.

5. The petroleum distillate as set forth in claim 2 being lubricating oil.

6. The solid additive as set forth in claim 1 which said epihalohydrin is epichlorohydrin.

7. The solid additive as set forth in claim 1 in which said primary amine is composed of a mixture of 4% C H alkyl amines, 29% C alkyl amines and 67% C alkyl amines.

8. The solid additive as set forth in claim I in which said primary amine is composed of a mixture of I07: C alkyl amines and 90% C -C alkyl amines.

9. The solid additive as set forth in claim 1 in which said primary amine is composed of a mixture of 20% C alkyl amines, 30% C alkyl amines and 50% C -C, alkyl amines.

10. The solid additive as set forth in claim I in which said N-alkyl-l ,3-diaminopropane is composed of a mixture of 4% C 29% C and 67% C N-alkyl-l,3- diaminopropanes.

1 l. The solid additive as set forth in claim 1 in which said N-alkyl-l ,3-diaminopropane is composed of a mixture of 10% C and 90% C -C N-alkyl-l ,3-diaminopropanes.

12. The solid additive as set forth in claim 1 in which said N-alkyI-l ,3-diaminopropane is composed of a mixfuel oils or on the inside parts of engines in the case 0f ture of 20% C 30% C and 50% C -C N-alkyllubricating oils will be greatly diminished.

I claim as my invention:

l ,3 -diaminopropanes.

1' i I 1 t 

1. A SOLID ADDITIVE COMPRISING A MIXTURE OF FROM ABUT 1 TO ABOUT 50 PERCENT BY WEIGHT OF THE REACTION PRODUCT OF AN EPIHALOHYDRIN AND A PRIMARY AMINE CONTAINING FROM 14 TO 22 CARBON ATOMS, AND FROM ABOUT 50 TO ABOUT 99 PERCENT BY WEIGHT OF THE REACTION PRODUCT OF AN EPIHALOHYDRIN AND AN N-ALKYL-1,3-DIAMINOPROPANE CONTAINING FROM 14 TO 22 CARBON ATOMS IN THE ALKYL CHAIN.
 2. THE SOLID ADDITIVE AS SET FORTH IN CLAIM 1 BEING ADDED TO A PETROLEUM DISTILLATE.
 3. The petroleum distillate as set forth in claim 2 being gasoline.
 4. The petroleum distillate as set forth in claim 2 being fuel oil.
 5. The petroleum distillate as set forth in claim 2 being lubricating oil.
 6. The solid additive as set forth in claim 1 which said epihalohydrin is epichlorohydrin.
 7. The solid additive as set forth in claim 1 in which said primary amine is composed of a mixture of 4% C14 alkyl amines, 29% C16 alkyl amines and 67% C18 alkyl amines.
 8. The solid additive as set forth in claim 1 in which said primary amine is composed of a mixture of 10% C18 alkyl amines and 90% C20-C22 alkyl amines.
 9. The solid additive as set forth in claim 1 in which said primary amine is composed of a mixture of 20% C16 alkyl amines, 30% C18 alkyl amines and 50% C20-C22 alkyl amines.
 10. The solid additive as set forth in claim 1 in which said N-alkyl-1,3-diaminopropane is composed of a mixture of 4% C14-, 29% C16-, and 67% C18 N-alkyl-1,3-diaminopropanes.
 11. The solid additive as set forth in claim 1 in which said N-alkyl-1,3-diaminopropane is composed of a mixture of 10% C18-, and 90% C20-C22 N-alkyl-1,3-diaminopropanes.
 12. The solid additive as set forth in claim 1 in which said N-alkyl-1,3-diaminopropane is composed of a mixture of 20% C16-, 30% C18-, and 50% C20-C22 N-alkyl-1,3-diaminopropanes. 